Smoking tobacco including releasable flavorant



United States Patent 3,353,542 SMOKING TOBACCO INCLUDING RELEASABLE FLAVORANT Keith D. Kilburn, Southampton, England, assignor to Brown and Williamson Tobacco Corporation, Louisville, Ky., a corporation of Delaware No Drawing. Continuation of application Ser. No. 429,672, Feb. 1, 1965. This application May 18, 1967, Ser. No. 639,585

8 Claims. (Cl. l3117) This application is a continuation of application Ser. No. 429,672, filed Feb. 1, 1965, and now abandoned.

This invention concerns improvements relating to smoking tobacco and seeks to provide a method of improving the flavour and aroma or taste of tobacco smoke.

Substances are known which can be added to tobacco to improve the flavour and aroma, for example menthol, but it is a characteristic of most such substances that they are readily volatile. On lighting a cigarette made from tobacco containing suchsubstances, the flavour substance or its effect may therefore be lost before the smoking of the cigarette is complete, so that the agreeable or beneficial effect is no longer apparent in the last or later puffs. Accordingly, it would be advantageous if the substance to be added to tobacco could be applied in a less volatile form, so that the flavour might last throughout the smoking of the cigarette or tobacco.

An object of the present invention is to provide for substances which enhance the flavour of the smoke to be released progressively to the smoke stream.

According to the invention, one or more titanium alcoholates or, more precisely, esters of orthotitanic acid is or are added to tobacco or to a tobacco-smoke filter or tip material. For improving the flavour of cigarette to-' bacco, in particular, such an ester or esters may be added by spraying or dusting to the cut tobacco before the finished cigarette is formed or to cigarette filter or tip material. During smoking of a cigarette made with tobacco, or provided with a filter or tip, which has such an addition, the heat generated and/or the smoke constituents produced, by the combustion of the tobacco progressively flavour and aroma propertiesof a tobacco can be effectively modified by readily available substances and by simple means. I

Esters of orthotitanic acid of the general formula (RO) .Ti, in which R may be an alkyl or cycloalkyl radical which contains more than five carbon atoms or may be an aralkyl radical, are more especially suitable for application to cigarette filter tips. For this purpose, they may be added, for example, in an amount equivalent to 0.1 to 20 mgm. per tip, preferably 0.5 to 3.0 mgm. per tip, in the case of the menthyl ester and in an amount of 3 to 200 microgm, preferably 5.0 to 50 microgm, per tip in the case of the linalyl or phenylethyl ester. The esters can be applied, for example, by spraying fibrous tip material with a solution in a solvent such as acetone, petroleum ether or diethyl ether. In the case of a tip material such as cellulose acetate, the ester may alternatively be incorporated in the plasticiser.

The above-mentioned esters are less suitable for application to tobacco, because they are not always reliably stable in the presence of moist tobacco. However, more complicated esters of orthotitanic acid are very stable and serve excellently as additives to tobacco, including reconstituted tobacco, although this stability renders them considerably suitable for addition to filters. Examples of such more complicated esters are the reaction product of tetramenthyl orthotitanate 01' of di-n-butyl dilinalyl orthotitanate and hexane-1:6-diol. Theoretically such compounds might be expected to have a general formula of the type (R O) .Ti.(OR in which R 0 is a flavour alcohol group, such as menthyllinalylor B-phenylethyL, forming part of the total alcohol content, while R 0 is another polyhydric alcohol group, preferably one comprising at least two primary or secondary alcohol groups, forming the other part of the alcohol content. Whether the aforesaid general formula is always or strictly correct, these more stable esters release the flavour alcohol on smoking ofthe tobacco. They also release the diol, or triol or a derivative produced in the smoking process, which gives enhanced flavour to the tobacco smoke in addition to the distinctive flavour of the flavour alcohol.

The amount of the orthotitanic-acid ester added to tobacco may be up to 3 gm. per gm. of tobacco (including moisture), but is preferably not more than 1 gm. per 100 gm.

Examples of ways of carrying the invention into effect by the addition of the ester to tobacco will now be more fully described:

Example I.--Telrantenthyl orthotitanate 74 gm. (0.22 mole). of tetra-n-butyl orthotitanate was placed in a dry flask fitted with a dry fractionating column and distillation unit. 136 gm. (0.88 mole) of menthol was added and the mixture heated. When reflux began in the fractionating column, the whole column was heated to C. by a heating tape applied to the column. Heatin g of the flask and the column was continued until almost the theoretical weight, 64 gm., of butanol had been distilled. The remaining butanol was removed by the application of a slight vacuum to the system for a few minutes. 144 gm. of tetramenthyl orthotitanate was obtained.

Cigarettes were prepared from tobacco containing 0.2 gm. of the orthotitanate in IOO'gm. of cut tobacco, to which the orthotitanate was applied in solution in acetone. On smoking a cigarette so prepared, menthol was smoothly and progressively released-and the menthol flavour was noticeable throughout the smoking.

Example Il.- Te t ralinalyl orthotitanate Example Ill-Tetramenthyl orthotitanate/hexane-l:6- -di0l reaction product 17.6 gm. of tetramenthyl orthotitanate prepared as an Example I was dissolved in 80 ml. of acetone, previously dried over anyhdrous sodium sulphate. To this solution was added a further solution, also dried over anhydrous sodium sulphate, of 6.2 gm. of hexane-1:6-diol in 60 ml. of acetone sulphate. A heavy white precipitate formed and was separated by filtration. After washing with five separate 50 ml. portions of dry solvent, the precipitate was 6.8 gm. of an odourless white solid. On analysis, this was found to contain titanium, menthol and hexane- 126-diol in combination. Analysis of the residual filtrate after separation of this compound showed that no unreacted hexane-1:6-diol remained, but 13.7 gm. of men-' thol was present. The solid product was found to generate menthol on heating at SOD-340 C. in the presence of steam.

On smoking cigarettes made from tobacco to which this product had been added, in a proportion of 0.5 gm. per 100 gm. of tobacco, by spraying with a suspension in acetone, a marked improvement in the flavour characteristics of the smoke was noticeable in addition to the menthol flavour which persisted throughout the smoking.

Example lV.Di-n-butyl dilinalyl orthotitanate/hexane 1:6-di0l reaction product 10.1 gm. of tetra-n-butyl orthotitanate and 9.1 gm. of linalool were stirred together at 70 C. under a partial vacuum (25 mm. Hg). Reaction took place and n-butyl alcohol was evolved and collected. When the evolution of n-butyl alcohol ceased, 140 gm. of di-n-butyl dilinalyl orthotitanate remained in the flask as a slightly viscous yellow liquid.

1.53 gm. of heXane-1:6 diol was mixed with 3.23 gm. of the di-n-butyl dilinalyl orthotitanate produced as just described and the mixture was heated to 150 C. A vigorous reaction took place in which 0.80 gm. of butanol was evolved and 3.87 gm. of a waxy white solid was formed. After washing with five portions of 20 ml. each of diethyl ether, the waxy solid retained no odour of nbutyl alcohol or linalool.

n heating to BOO-340 C. in steam, the solid product was found to generate linalool readily. On smoking cigarettes made from tobacco to which this product had been added in a proportion of 0.05 gm. per 100 gm. of tobacco by spraying with a suspension in acetone, a marked improvement in the flavour characteristics of the smoke was noticeable, in addition to the linalool flavour which persisted throughout the smoking.

By the procedure described in Example III, diol or triol compounds other than the hexane-1:6-diol compound can be produced. Alcohols found to be suitable for forming esters for adidtion to cigarette tobacco are listed in the following table:

TABLE No. of OH Groups No. of Carbon Atoms Alcohol 1 Ethylene glycol 2 1:2 propylene glycol 3 1:3 propylene glycol 2:3 uutylene glycol 1:4 butanediol WMNMNNNNN t- OMFWOJWWWWN The compounds formed from 1, 2, 5, 6 and 9 were found to give particularly advantageous flavour effects. It will be noted that triethanolamine contains nitrogen as well as carbon.

An example for the adidtion of an ester of orthotitanic acid to a filter-tip material is as follows:

Example V I claim:

1. A smoking tobacco product having improved taste, flavor and aroma characteristics comprising a smoking tobacco device having a filter mouthpiece end and an ignition end, the device having incorporated therein a small amount of an ester of orthotitanic acid, the ester capable of being decomposed to yield a flavorant when the device is being smoked by the user.

2. A smoking tobacco product having improved taste, flavor and aroma characteristics as set forth in claim 1 wherein the ester is incorporated in the filter.

3. A smoking tobacco product having improved taste, flavor and aroma characteristics as set forth in claim 1, wherein the ester is selected from the group consisting of tetralinalyl orthotitanate, tetramenthyl orthotitanate, the reaction product of tetramenthyl orthotitanate and hexane-1,6-diol and the reaction product of di-n-butyl dilinalyl orthotitanate and hexane-1,6-diol, and beta-phenylethyl orthotitanate.

4. A smoking tobacco product having improved taste, flavor and aroma characteristics as set forth in claim 1, wherein the ester is incorporated in the filter and the ester is selected from the group consisting of esters having the general formula (RO) .Ti

and esters having the general formula (R O)x.Ti.(OR )y in which R is an organic radical containing more than five carbon atoms and is selected from the group consisting of alkyl and a cycloalkyl and in which R is a flavor alcohol radical and R is a polyhydric alcohol radical.

5. A smoking tobacco product having improved taste, flavor and aroma characteristics comprising smoking tobacco having incorporated therein a small amount of an ester of orthotitanic acid, said ester capable of being decomposed by the heat of burning tobacco to yield a flavorant to be carried by the smoke to the user.

6. A smoking tobacco product having improved taste, flavor and aroma characteristics comprising smoking tobacco having incorporated therein a material selected from the group consisting of tetralinalyl orthotitanate, tetramenthyl orthotitanate, the reaction product of tetramenthyl orthotitanate and hexane-1,6-diol and the reaction product of di-n-butyl dilinalyl orthotitanate and hexane-1,6-diol, and betaphenylethyil orthotitanate.

7. A smoking tobacco product having improved taste, flavor and aroma characteristics comprising a smoking tobacco having incorporated therein an ester of orthotitanic acid selected from the group consisting of esters having the general formula (RO) .Ti

and esters having the general formula (R O)x.Ti.(OR )y in which R is an organic radical containing more than five carbon atoms and is selected from the group consisting of alkyl and a cycloalkyl and in which R is a flavor alcohol radical and R is a polyhydric alcohol radical.

8. A method for imparting a flavorant to a tobacco smoke stream which comprises adding a small amount of an ester of orthotitanic acid to smoking tobacco, and then burning the said tobacco to decompose the ester and rerelease the flavorant for entrainment in the smoke stream.

References Cited UNITED STATES PATENTS v 3,288,146 11/1966- Bauley et a1. 131200 X SAMUEL KOREN, Primary Examiner.

MELVIN D. REIN, Examiner. 

5. A SMOKING TOBACCO PRODUCT HAVING IMPROVED TASTE, FLAVOR AND AROMA CHARACTERISTICS COMPRISING SMOKING TOBACCO HAVING INCORPORATED THEREIN A SMALL AMOUNT OF AN ESTER OF ORTHOTITANIC ACID, SAID ESTER CAPABLE OF BEING DECOMPOSED BY THE HEAT OF BURNING TOBACCO TO YIELD A FLAVORANT TO BE CARRIED BY THE SMOKE TO THE USER. 